Manufacture of catalysts



Pmmd Mar. 1, 1949 umrso STATES PATENT. OFFICE MANUFACTURE or CATALYSTS Glenn M. Webb and Marvin A. Smith, Riverside, 111., asslgnors to Universal Oil Products Company, Chicago, 111., a corporation of Delaware N Drawing.

Broadly the present invention comprises the preparation of associations of alumina and other catalytic substances by forming a hydrated a1umina from an aluminum salt having the aluminum in the cation, combining said alumina with an aqueous solution of a compound constituting the source of the other catalytically active compound in the final composite, said compound being characterized in that the metal is present in the anion radical and that the cation group is volatilizable, evaporating the mixture to dryness and heating the resultant composite to develop its catalytic properties.

The process of the invention is particularly applicable to the production of catalysts in which alumina is a major constituent and oxides such as molybdic oxide are minor constituents. Such catalysts are particularly useful in various hydrocarbon conversion reactions including reforming petroleum fractions with or without added hydrogen. Alumina-molybdena catalysts are particularly useful in the so-called hydroi'orming" process in which hydrocarbon fractions such as naphthas together with hydrogen are treated in the presence of the catalysts to increase the antiknock value, preferably without substantial consumption of hydrogen.

The alumina hydrogel may be combined with the other catalytical compounds by various methods. We have discovered that superior catalysts can be produced by the following methods oi. preparation.

METHOD I The composites comprising associations of alumina and other catalytically activesubstances, particularly oxides, are prepared by partially or completely precipitating hydrated aluminum oxide by means of a volatilizable basic precipitant from a solution of an aluminum salt, thereby forming from the acid radical of said aluminum salt, and said precipitant, a salt which is readily volatilizable or decomposable without residue,

said precipitation being efiected in the presence.

Application September 27, 1944, Serial No. 555,092

6 Claims. (Cl. 252-465) of a compound yielding the said other catalytical ly active substance and containing a metal in its anion radical, thereafterevaporating the solution to substantial dryness, and further heating the residual material thus obtained to volatilize the a salt of the precipitant to produce the catalytic composite.

METHOD II The catalyst composite is prepared by adding a volatile basic precipitant to a solution of an aluminum salt and a compound capable of yielding the other catalytically active substance to form a precipitate of hydrated alumina by which at least a portion of said catalytically active compound is sorbed, washing said precipitate to remove at least a portion of soluble compounds other than said compound capable of yielding the catalytically active substance, and thereafter heating to produce a catalytic composite.

METHOD III The catalyst composite is prepared by adding a volatile basic precipitant to a solution of an aluminum salt under conditions of temperature, concentration of reactants and rate of addition which will form a gelatinous precipitate of hydrated alumina separating and washing said alumina under closely controlled conditions of pH,

without otherwise substantially drying it, to the substantially complete removal of soluble salts therefrom, suspending the washed alumina in water, adding a compound capable of yielding the other catalytically active substance to the suspension, heating the suspension to evaporate water and calcining to develop the desired catalyst.

As a specific modification of Method III, the precipitated hydrated alumina may be filtered from the solution containing it and incorporated into the solution of other catalytically active sub-- stance without the intermediate washing operation. The volatilizable salt formed by combining the cation of the basic precipitant and anion of the aluminum salt will be removed during the subsequent calcination step.

The foregoing briefly described procedure has been found to produce catalytic associations oi! alumina and other catalytic oxide substances which associations have superior catalytic activity in various organic reactions when compared with catalyst composites of similar chemical composition prepared by previously established methods of manufacture. Such methods as, 'forexample, the impregnation of prepared granular aluminas such as the "activated aluminas" of commerce with solution of compounds yieldasoao'ra manufacturing methods to which the present method is decidedly superior.

The catalysts produced by the present process have been found to be superior in catalytic activity both as regards initial activity andthe ability. of the catalysts to maintain their activity over periods of sustained use, with for without reBeneration, in comparison with composites of similar chemical composition prepared by the so-called co-precipitation processes. The co-precipitation gredients of the composite are formed either by interaction with one another or by the addition of precipitants to solutions containing both a compound of aluminum and a compound capable of yielding the desired catalytically active oxide.

In suchprocesses, the association is made by simultaneous precipitation of the components, usually followed by washing and heating the composite.

- The-present process has also been found to u 1 yield generally better catalysts than those produced by either the successive precipitation of alumina and the other catalytically active oxides or those prepared by suspending granular alumade, the tendency for the substance to vaporize or to migrate appears to be substantiallyreduced and as a result thereof,-a great improvement in the high degree of catalytic activity is realized throughout prolonged use.

In accordance with the present process, the hydratedv aluminum ,oxide is precipitated, from a solution of analuminum salt; that is, the aluminum is contained in the cation of the aluminum salts. 'Such salts may include salts of hydrochloric acid, hydrobromic acid, hydrofluoric acid, sulphuric acid, carbonic acid, nitric acid, acetic acid, oxalic acid, and other acids .which yield soluble aluminum salts. Aqueous solutions of methods include those in which-the essential in- 15 aluminum salts are generallypreferable. It is comprised within the scope of thein'ventionto employ solutions of aluminum salts in other types of solvents which are substantially inert or nonreactive with aluminum salts or other ingredients to be used in the preparation of the catalyst compositesas'described hereinafter. By inert or non-reactive, it is meant that the solvent shall not cause transformation of the ingredients into anundesirable form, or which may bring about an undesirable precipitation of the non-alumina ingredient. Mixtures of aqueous and non-aqueens-solvents may be'used in certain instances where the non-alumina substance is not'sufiiciently soluble in'water.

mine in solutions of such compounds and then go The volatilizable basic precipitants used in the causing precipitation of the catalytically active material. a I

- Many advantages of this process are derived from the simple procedural steps involved. 'One general advantage lies in the fact that there is an even distribution of the non-alumlniferous compound throughoutthe body of the alumina so that the catalytic surfaces are much more uniform than is the case when employing other more conventional types of processes. Thus, for 0 example, for a given degree of activity, it is found that the present catalysts tend to produce less carbonfor agiven conversion than is the case with catalysts of similar chemical composition niade, for instance, by impregnation of alumina. 45.

This is thought to be due to the fact that the catalytic surfaces are more uniform and that thereare no relatively large clusters or concentrations of the non-aluminiferous component at as may be the case with other alumina containing eomposites prepared either by co-precipitation or by impregnation methods. As a result, the overall activity is improved and the catalyst becomes more selective for the reaction it is to catalyze. 56 Another advantage of this method is found in I those composites falling within the scope of this invention wherein the added non-aluminiferous compound has an appreciable vapor pressure at t the. processing or reactivating temperature at 60 which the catalyst is used. Thus, for example, molybdena or 'chromia have appreciable vapor pressures at temperatures above 700 C. which temperature is often reached during the course T,

of either processing or regeneration, and the cat- 'alyst loses appreciable quantities of the substances associated with the alumina, or else there *may-bea substantial'migration oi the substances to other parts of the catalyst particles with res'ultant diminution of catalytic efllciency with prolonged use.

Because of the manner in .which the alumina and the added substance are composited and because of the extremely intimate association of present process include generally ammonium compounds having a basic reaction such as, for example, ammonium hydroxide, ammonium carbonate, etc. Also useful in accordance with the present invention are substituted ammonium compounds such as amines or nitrogen bases generally, insofar as the compounds formed between these substances and the volatilizable acids in association with aluminum are suillciently 'volatizvarious points through the alumina par 01 es .50. to above comprise compounds of the metals in the left hand columns of groups V and VI of the periodic table and particularly compounds which yield the oxides of chromium, molybdenum and vanadium in the final catalyst composite.

As a feature of this invention, the catalytically active compound to. be combined with the alumine. and which constitutes the source of the catalytically active compound in the composite catalyst is characterized by the fact that the metal constituents 'of said compound appears in the anion radical and that the cation group is volatile leaving the oxide of the-metal as the residue upon decomposition; for example, by heat- 1 ing or if a three-component catalyst is desired,

65. the cation group is either magnesium or zinc ion which upon decomposition form either magnesium or zinc oxide in the composite catalyst. Specific examples of these compounds are ammonium chromate, ammonium molybdate, ammonium vanadate, chromic acid, molybdic acid, vanadic acid, magnesium chromate, magnesium molybdate, zinc chromate or'molybdate and simi lar compounds. 1

The aluminum hydrogel prepared from the the catalyst components after the compositev is aluminum salts may be combined with the. other catalytically active compounds by various methods to produce superior. catalysts of substantially equivalent activity and thermal stability.

In previously mentioned Methods I and II, it is necessary to add a suflicient quantity of the precipitant to bring the pH to a value of at least about 4 to eiIect precipitation of a major portion of the hydrated alumina. In order to effect substantially complete precipitation of the hydrated alumina, it may be necessary to go to higher pH values even to the point 01' having the solution decidedly basic. The exact pH chosen in the preparation of any particular catalyst will depend upon the concentration of the aluminum salt solution and upon the characteristicsof the other ingrediit is necessary to maintain the solution distinctly on the basic side in order to prevent undersirable coprecipitation of the non-aluminiferous ingredients together with the hydrated alumina. Some ingredients may be soluble at substantially the neutral point while others may precipitate at this point but remain soluble in basic or acidic solution. Only such compounds as are soluble in water and/or other solvent in the presence ofthe volatilizable precipitant and the hydrated alumina should be employed since if precipitation of the compound to be associated, or co-precipitation occurs, the improvements will not be fully realized. This limits the compounds that may be added. In some instances there is a possibility of reaction between the alumina and the other compound. This does not mean that the aluminum salt and the non-aluminiferous salt have co-precipitated, but merely that some physical-chemical interaction such as the adsorption by the hydrated alumina may have taken place. We do not, however, intend to be bound unduly by any such explanation.

In certain cases wherein the added compound is suiiiciently soluble only at a pH of less than 7; or where it is desired to carry out the precipitation of alumina hydrate in a slightly acid system it may be that the pH will be inadvertently carried too high. It may be adjusted by adding a small amount of an acid to the system. Alternatively, a small amount of the aluminum salt may be added. This makes the operation somewhat more flexible in that no great harm is done at this stage if optimum conditions are not at+ tained the first time.

In certain cases it may be desirable to precipi tate the alumina substantially completely by carrying the pH over to the basic side and thereafter bring the pH back to the acid side bythe addition of an appropriate acid, for example, acetic acid or hydrochloric acid. Such a procedure may be followed in accordance with the principles of this invention especially when the compound constituting the source of the nonaluminiferous catalytic substance is soluble in either basic or acidic solution. Thus, for example, one may make a solution of aluminum chloride and ammonium molybdate. A sufiicient quantity of ammonium hydroxide may be added to bring the pH to about 8 thereby completely precipitating the alumina as hydrated aluminum oxide. If a comparatively concentrated solution ofthe aluminum salt is used originally. the hydrated alumina may coagulate and form a more or less rigid gel or particles of gel, which tend to separate upon standing.

To overcome the tendency toward non-uniformity, acetic acid, for example, may be added until the pH is on the acid side and part of the alumina is converted to ahydrosol.

From this point on the procedure of Methods I and II differ considerably. In Method 1, the next step of the catalyst manufacture comprises heating the suspension of hydrated aluminum oxide in the solution containing the non-aluminiferous ompound (as well as salts of the basic precipitant and the acid radical of the aluminum salt) to drive oil water (or other solvent Hall is used) and leave a residual relatively dry solid material.

In the next step the residual mass is heated at higher temperatures generally not exceeding 900 C. to remove by volatilization or decomposition the reaction products resulting from the precipitation of aluminum hydrate; to drive oi! the remaining free water and at least a part of the bound water; and to develop the catalytic properties of the composite.- This may involve, in part, decomposition of the .non-aluminiferous compound present into the oxide or other substance which is to be present in the final catalyst composite. When ammonium compounds have been used as the precipitants for the hydrated alumina in the primary stage of the process, the materials volatilized will be ammonium salts. For example, if ammonium hydroxide has been added to a solution of aluminum chloride'the principal material volatilized in the final heating stage will be ammonium chloride. If volatile organic acids such as acetic acid have been present, or aluminum acetate were used in the preparation, some carbon may be present inthe dry, solid mass due to decompositionof the organic material. In such a case it is desirable to carry out the final heating step in the presence of an oxygen-containing gas to burn out the carbon.

Ordinarily, calcination temperatures below approximately 900 C. and sometimes temperatures as low as about 200 C. may be employed in the final heating step. The exact temperature and time of heating used for any given catalyst preparation is dependent to a large extent upon the volatilization temperature of the salt of the basic precipitant; the use to which the catalyst is to be put; and upon other factors such as the decomposition temperature of the non-aluminiferous compound to yield the associated catalytic oxide or substance. In many of these preparations, care must be taken to avoid overheating of the composite. Thus, for example, when preparing catalysts for the dehydrogenation of dehydrogenatable organic compounds, temperatures in excess of about 900 C. should be avoided,

and it the heating is carried out at such a temperature, the time of heating should be limited so that substantially no loss in catalytic activity occurs due to overheating. The correlation of time and temperature is always an important consideration in calcining catalysts. particularly when temperatures of the order of 700 C. or

f higher are used. It is a .feature of any of the catalysts produced by the process of the present invention that they withstand higher temperaadvertent overheating. In general, heating conditions which result in the transformation of aseaova 7 alumina to the alpha avoided.

The final catalyst composite, after the calcina ious shapes by compression or extrusion methods.

In forming'pelleted catalyst from the catalytic material after the volatilization of the salts in the final stopof preparation, the solid residue may be ground'to' a desired size and a small percentage of lubricating materials such as rosin or fatty substances may be added to facilitate pilling in standard type of machines. Usually such pellets are later calcined at sufflciently elevated temperatures to remove the lubricant. As a further variation certain ofv the dried composites may be formed into shapes after drying, and the calcination step may then be carried out on the preformed particles.

In Method II, following the precipitation of the hydrated alumina which is carried out under such conditions that the hydrated aluminum is in a fllterable and washable form, usually gelatinous and the other compound is sorbed at least in part by the hydrated alumina, the precipitate is washed by any suitable method such as by decantation, percolation or slurrying followed by either decantation or filtration until Pat least a portion of soluble salts is removed, while retaining a portion'of thesorbed compound serving as -the source of the other catalytically active substance. The salts, which it is desired to remove, are those resulting from the precipitation of the alumina and comprise the anion of thealuminum salt and the cation of the basic precipitant.

The washed material is now heated undercontrolled temperature conditions to;vo1atiiize the volatilizable constituents and to develop the catalytic properties of the composite. In this step the residual mass is heated at higher tempera- Y tures generally not exceeding 900 C. to remove alumina form are to be able precipitate of hydrated alumina is formed.

The concentration of the aluminum salt may vary over a considerable range but is usually within the range of 1 gram molecular equivalent of aluminum chloride hexahydrate in from about 1- to 5 liters of water. Concentrated solutions of precipitant such as ammonium compounds, may

.be used in the precipitation which may be conducted at temperaturesof from about to about 90 C., and precipitation is preferably conducted during vigorous stirring so that the precipitate is obtained in a relatively finely divided condition.

The precipitant is added until a pH value of from about to about 8.5 is produced and at this time the precipitate is separated and washed to remove a substantial portion of soluble salts. A1-.

ternatively, with the precipitation of the hydrated alumina as a flnelydivided gelatinous hy- I preferably conducted with water having a pH.

by volatilization or decomposition any remaining drated material, a sol may be produced which is allowed to gel and the gelbroken up for the washing step.

In the next step the precipitated wet hydrated alumina is filtered and washed by any suitable method such as by decantation, percolation or alternate slurrying and filtering. Washing is close to '7 to prevent increase in size of. the alumina particles which may occur if water having a p11 higher than this is employed. If pH values lower than 'I are employed, there will be a tendency of re-solution of the alumina. Washing may be conducted until substantially all of the ammonium salts are removed, although if minor amounts are left, they will be volatilized or decomposed into volatile products. in subsequent heating and calcining steps hereinafter described. a

The washed and purified alumina may now be suspended in water to fornra slurry and a compound is dissolv'ed in the suspending medium which is capable of yielding the desired catalytically active material. After athorough mixing to insure intimate contacting of the alumina par- I ticles and the solution ofthe. dissolved comties ofthe composite. This may involve, in part, 1

decomposition of the non-aluminiferous com- "pound present into the oxide or other substance which is to be present in the final catalyst comi posite. When ammonium compounds have been used as the precipitants for the hydrated alumina in the primary stage of the process, the materials volatilized may comprise ammonium salts. Ordinarily, calcination temperatures below approximately 900 C. are employed in the final heating step. The exact temperature and time of heating used for any given catalyst preparation is dependent to a large extent upon the volatilization temperature of the salt of the basic precipitant whenthe washed precipitate contains this salt; the use of which the catalyst is to be put; and upon other factors such as the decomposition temperature of the nonaltuniniferous compound to yield the associated catalytic oxide or substance. In general, heating conditions which result in the transformation of alumina to the alpha form are to be avoided.

. In Method III of thepresent'invention, the

first step involves the precipitation of a hydrated alumina'from a solution of an aluminum salt using volatile basic precipitants similar to those employed in Methods I and II. The conditions under which precipitation is brought about are preferably controlled so that a gelatinous, filter pound, the total mixture is heated to evaporate the water. Temperatures which can be employed in the final drying may range from about 250 to about 500 F. After the volatile content of the residue from the evaporation is reduced to about 10%, the mass may be heated todevelop its cata-' lytic properties. An elevated temperature within the range of from about 1000 to about 1500 F.

is usually best to.-develop the desired catalytic properties. The material at this point will be either a powder or a material readily powdered and may be used as such or after forming into pellets or granules by extrusion or pressing methods. The catalytic material thus produced is substantially free from undesirable contaminating substances and shows high catalytic activity.

The catalytic composites formed by Methods I, II and III may be contacted with solutions of compounds of calcium, strontium, or barium to incorporate small proportions of these materials which can be subsequently converted to the oxides to produce multi-component catalysts.

The conditions of operation which may be employed when these catalysts are used in dehydrogenation operations depend to a large extent upon the type of catalyst. that is used, the material being dehydrogenated, the extent of dehydrogenation that is desired, and upon various other factors. Generally speaking. in the case of reforming gasoline fractions or naphthas in the I presence of hydrogen, 1. e., in so-called "hydroforming," temperatures in the rang of from about 450-750" C. pressures in the range of from atmospheric to 40 atmospheres or more; liquid hourly space velocities usually below about 10 and preferably in the range of from .1 to and molal ratios of hydrogen to charging material in the range of .2 to 8 are usually employed. In general, relatively high space velocities are used at relatively high temperatures within the ranges indicated, .and at any given temperature a relatively high space velocity may be used with a relatively high pressure. In this process, any hydrogencontaining gas (oxygen free), preferably one predominantly hydrogen, may be employed. Since a net production of hydrogen results from the hydroforming" process, a part of the process gases may be recycled.

By the term liquid hourly space velocity as herein used we mean the volumes of hydrocarbon measured as liquid at normal temperature, per bulk volume of granular catalyst per hour.

The term gas hourly space velocity as used herein refers to the volumes of hydrocarbon measured as a gas at standard conditions of temperature and pressure, per bulk volume of granular catalyst per hour.

If the reaction is carried out in the presence of powdered catalyst moving through a reaction zone, the ratio of catalyst to hydrocarbon may be expressed in appropriate terms corresponding to the conditions expressed by these definitions. 1

In the case of -catalytic reforming wherein hydrogen is not used the operating conditions may otherwise be substantially the same as in the "hydroforming process. I

In aromatizing a hydrocarbon consisting of or containing aliphatic hydrocarbons having 6 or more carbon atoms per molecule, the operating conditions may be as follows: temperatures in the approximate range of from 450-700 C}; pressures varying from atmospheric to 10 atmospheres or more, and liquid space velocities usually less than about 10 and preferably ranging from about 0.1 to 5. In this type of operation it may in some case be desirable to supply or recirculate hydrogen or hydrogen-containing gas to the reaction zone. j

In the dehydrogenation of naphthenes containing 6 carbon atoms in a ring, temperatures ranging from 250 C. to 650 C., liquid space velocities in the range of from about 0.1 to about 20, and pressures ranging from atmospheric to 10 atmospheres or' higher may be used. Usually, the charging materials for aromatization processes are stock which consist not only of straight chain aliphatic hydrocarbons but also of naphthenes containing 6 carbon atoms in a ring. For: this reason, when operating on a charge containing both aliphatic hydrocarbons and naphthenes, conditions for the aromatization of the aliphatic hydrocarbons are employed, if it is desired to I form aromatics from the aliphatics as well as from the naphthenes.

In dehydrogenating aliphatic hydrocarbons into corresponding less saturated aliphatic hydrocarbons such as dehydrogenating parafilns to form olefins; mono-olefins to form diolefins; and

In dehydrogenating butane or butene or butane-butene mixtures to butadiene, the temperatures may range from 450 to 700 C., the gas space velocities from 200 to 3000, and the pressure, atmospheric, but preferably substantially subatmospheric. The partial pressure of "the C4 hydrocarbons is usually kept below 300 mm. mercury absolute, preferably between 15 and 250 mm. mercury absolute, in order to prevent undue decomposition of the butadiene. The partial pressure of the hydrocarbon may be reduced by use of steam or other inert gases in some cases.

In the dehydrogenation of thylbenzene to form styrene, the temperatures may range from 450-700" C., and the liquid space velocities from 0.1

to 5. Low pressures are preferred, ranging from 0.1 to 2 atmospheres. In this case the partial pressure of the ethylbenzene may be reduced by steam or other inert gas.

In general when dehydrogenating organic compounds according to the present invention, temperatures and pressures to be employed may be of the order of those heretofore employed in like reactions.

The following are specific examples of the preparation of catalysts and their use in specific embodiments of the present process.

EXAMPLEI Hydroforming of low octane number gasolines according to the invention using an aluminamolybdena composite as catalyst prepared in accordance with our preferred method is considered in comparison with the use of catalysts prepared by the conventional procedure of impregnating prepared granules of alumina with compounds yielding molybdenum oxides.

In the preparation of the presently preferred type of catalyst aluminum chloride hexahydrate is dissolved in water, one liter of water being used per gram mole of the compound A1Cl3.6H2O. To such a solution an amount of ammonium molybdate is added so that in the finally prepared catalyst there is a weight percentage of molybdenum oxides calculated as M003 equal to about 7 per cent of the total composite. During thorough agitation of the solution varying amounts of ammonium hydroxide may be added to produce different pH values corresponding to the precipitation of substantially all of the dissolved aluminum salt as hydrated aluminum oxide. The suspension pf hydrated aluminum oxide in the ammonium molybdate'solution is then heated to drive off water and produce 'a residual solid mass which in each case is then heated to a temperature of about 370 C. to about 400 C., ground to pass a 30 meshsieve, mixed with 4 per cent by weight of rosin and formed into 7 8" by $4 pellets. To free the pellets of rosin and a major portion of the combined water, they are heated in the presence of air at about 600 C. for about two hours and,v then at above 750 C. for approximately 6 holirs.

g The catalyst thus prepared is compared with another catalyst manufactured in substantially identical manner except that no ammonium hydroxide is added during the preparation. The catalyst is further compared with one made by impregnating by $4," pellets of an activated alumina of commerce with ammonium molybdate solution followed by drying and calcining under substantially the conditions used above. The concentration of molybdenum oxides in the calcined composite correspond to that of the other two catalysts. The catalyst is typical of those used 'lrecipitsnt. .Q .---.i-.

life of the catalyst has been worked out, but ex-, perience has shown-that the catalyst having the I higher activity after such calcinatio'n is for commercial purposes.-

superior cacao" in commercial hydrotormlng operations except that it is calcined at a higher temperature than 1 is ordinarily used. 1 Experience has shown that the-behavior el tists, alystscalcined at 750 C.-for'6 hours and :then.- tested for activityunder the conditions shown is a qualitative evaluation of the ability 'oi'the cata lysts to stand up under long periods operation: No absolute correlation between the test and the.

.i'ormed number gasoline.- Moreover, less carbon ,is

the conventional impregnatcd 0515 19 a plant oi. given :catalyst capacity; ouldgbef doubled in .reiorming capacity while a better Catalysts prepared in the manner described are 5 tested for hydroforming activity in the treatment of. a Mid-Continent naphtha fraction boiling from 103-207 C. and having an A. B. T. M. octane number 01 The prepared catalystpellets are placed in tubular reactors, and the vapors oi the naphtha mixed with about 4.5 moles of hydrogen per aver sure of 7 atmospheres, and velocity of 0.5. x The results are'shownin Table I.

. age mole of naphtha are passed through the catalyst at a'temperature of about 505 C at a a liquid hourly l,

' ismaint'ained over longer'periods or use. higher 1' octane numbers may be obtained with our 5 @Tsstll mation,

quality product; i f t 01117 benefit the requirements ,jior regeneration facilities in connection with the plant are materially reduced less of the charging'stock is lost through carbon formation; less time required for regeneration and conversely, more time is available for processing; fewer and. less severe regenerations are required which is a factor favoring economy and longer catalyst life. In addition to the iactthat the catalyst activity catalyst than is the case with" catalysts produ the impregnation method;.

Comparative dataon alumina -molybdena catalysts in hudroformina Final H Value Cal g Temp., C... Yield oi Gasoline, Volume Per cent Octane No. oi l0 Pound R. V. PJ Gasoline Carbon, Wt. Per cent NHIOH Reidvaporpressure. v The catalysts made by the present process more active than catalysts oi the same chemical composition made by evaporating solutions of salt of the components and calcining the residue,

or byfthe conventional impregnation process.

' This fact is evidenced by the higher octane numbers of the reformed gasoline. I r The data establish the superiority of theprocess oi this invention.

To further establish the superiority of our piefe'rred operation, our catalystis compared with the impregnated catalyst calcined at 800' (3.101 61 hours. 'Under thesev conditions the maximum activity of the impregnated catalyst is developed.

The results are shown in Table 11.

By our process it becomes double the space velocity (halt the contact time)- possible to employ l a g The tollowing illustrates hydroi'orming with catalystsoonsistin'g oi associations oi alumina and vanadia in our process asjcompared to the use oi catalysts 0! similar chemical, composition but made by impregnating activated alumina. The alumina-vanadia catalyst is made by preparing an ammoniacal solution of ammonium vanadate and adding it to a solution 01' aluminum chloride. The; amount or ammonia added is such that a maiorproportion of. the aluminum precipitates as hydrated aluminum oxide while the vanadium compound remains in soluble form,

After evaporating the solvent, the residual material is heated at 600{ C. to produce a composite containing .5 per cent y. weight of vanadium oxidescalculated at VsQs. 4

impregnated catalyst 'ior comparison is made by adding aqueous ammonium vanadate solution to commercial activated alumina similar to that used in Example I, and calcining at 600 C.-

The hydroiorming of a Mid-Continent naphtha with these catalysts is carried out at 525 0.; liquid space velocity 0.75; '6 mol hydrogen (based on the hydrogen content of recycled process gas) per mol oi=gasoline;=and pressure of 20 atmospheres. our process yields about '15 per cent of 85 octane number. gasoline.

impregnated catalyst yields '16 percent oi 80 octane number gasoline. The weight percentages or carbon on the catalysts are.0.9 per cent and 1.0 per cent respectively.

and produce'ahigher yield oi higher octane.

than is thecai'ie with the impregnated 1 "damperlin according to the inventmmmgm of th aliz'ed. f Because I or lower c'a'rbon ior- The use of the 13 EXAMPLE III Dehydrogenation of butane and butylene to butadiene is carried out by our process. In order' to operate at a reasonably low elflctive temperature and at a pressure not lower than is necessary and consistent with good conversion a catalyst of high activity and low carbon forming tendency is used. Catalysts suitable for this I purpose include alumina associated with molyb- 14 a major proportion of the alumina without, however, rendering the chromium compound unsoluble. The mixture is then evaporatedto sub- Tum: m

Dehydrogenation of butane-butane mixture to lmtadiene Bun No.

Catalyst Impregnated Improved I v88 A110: 927 AlaO; 52 9.33 8% Mo0a 12;; CrrOa 8% Mo0;

Cale Temp., 0 700 700 700 100 Process emp., C 675 675 675 675 Process pressure mm. H 80 80 80 80 Gas Hourly osiace Veloc ty 1,300 1,300 1,300 1,300 Process Peri Minutes 30 30 80 30 Yield oi Butadiene, Wt. percent:

Once Through 23 24 25. 27 Ultimate Yield Based on Recycle 70 68 84 86 Carbon, Wt. percent 2-34 1.96 1.4 1.32

dena, chromia, vanadia. and ceria. .These may be associated with oxides of zinc, calcium." strontium, barium and magnesium. The relative proportions of alumina and the added oxide or oxides depend to a large extent upon which catalytic substance is employed. Ordinarily the alumina comprises the major constituent. Smaller amounts of molybdena are preferred than is the case with chromia. The amount of chromia is usually from about 2 to about 40 per cent, while as a rule the best results are obtained with less than per cent molybdena in the composite catalyst.

In Table III are shown comparative results employing impregnated catalysts and those preierred in the process of our invention.

The impregnated catalysts are made according to the general procedure of soaking activated alumina in a'solution of a compound of the added substance, drying and calcining. catalyst in run #10' is prepared from activated alumina, chromic acid, and magnesium chromate. The alumina-molybdena catalyst of run t ll Thus, the

The data show that there is a substantial improvement in the amount of butadiene produced when using the improved catalysts.

is prepared by soaking altivated alumina with by forming a solution of alumina chloride and chromium nitrate. Thereafter suflici'ent quantity of ammonium hydroxide is added to precipitate both on a once-through and on a recycle basis Furthermore, less carbon is formed in the case of the improved catalysts than in thecase of the impr'egnated catalysts. The advantages of such an operation are apparent both from the stand- :point of conversion and plant costs.

Furthermore, the improved catalysts retain their activity for a much longer time than in the case of the impregnated catalysts. At a point at which the impregnated catalysts drop in activity so that a once-through yield of about 12 per cent of butadiene is obtained the operation with the improved catalysts produces more than 20 per cent per pass.

EXAMPLE IV Parafiln hydrocarbons containing at least 6 carbon atoms may be converted in accordance with the invention into aromatics by treatment with the catalysts of the character described. For this purpose the catalysts comprising alumina in association with diflicultly reducible oxides having more than one valence state are suitable. Oxides of elements selected from the lefthand columns of groups IV', V and VI are especially useful. or the preferred individual components associated with alumina, the oxides of molybdenum, chromium, vanadium, tungsten, and cerium are examples.

Table IV illustrates comparative results when a n-heptane fraction obtained by distillation of mineral oil is cyclicized with the improved catalysts of our process and catalysts produced by impregnation of activated alumina under average 7 M ma w I. "",RnnNo.

l ff onv :1.

"c tal st 1 i pregnated Improved stoluiollm Y a j j 22; 3%130! V Oaloining'lemp. =0 000 an I mun; Con flan! m m m m '1 l 1 1 -o.s 0.5 0.5 as v 4 4 4 4 1s 1s .74 4a at ca -02 as v 3.0a 1.3 1.6

Larielytolueney The results in the table show that the opera alysts the actual amount 0! carbon formed is a. P. 1.- gravity. co -r 52.8 Initial boiling point, F 217 End-point, =2 404 Octane number -I.-.... 34.6

substantially less. Because 01' the relatively high temperature used in the cycliz'ation it is desirable to use a catalyst having a good stability over extended periods of processing and regeneration.

an advantage realized in the case otour improved catalyst. EXAMPLE V The catalyst for this example was prepared in a the following manner: Ammonium hydroxide was added to a solution or 1 gram molecular equiv-' alent of aluminumchloride hexahydrate ina m mu camvuc wwtfl.mt droxide was used and the addition was made over Y liter of water. Concentrated ammonium hya period or about one hour until the pH was 6.7. At this point the precipitate was filtered in a pressure filter and the wet hydrogel reslurried in about 1 liter of water and-the operation or filtering and reslurrying was repeated twelve times. The wash water used was maintained ata pH value close to 7. The gel was not permitted to dry other than by expressing the water held therein. It contained about 85% of water.

'The washed wet hydrated alumina was then slurried in a liter of water and a 20% solution oi ammonium molybdate and thoroughly mixed with the slurry. The water was then evaporated and the residual material was heated at a tempera-p umn 2 contains the corresponding figures obture of about 250? F. to remove most ofthe wa-- ter, and then ground to pass a 30 mesh sieve,

mixed with 4% rosin, formed-into x cylinchine and heated to a temperature of about 1500 F. for six'hours. Its composition was then-' alumina 93%. molybdenum oxide 7%.

A catalyst was prepared for comparative pur- I procedure was substantially the same, and the alumina-molybdena ratio was the same as for the.

catalyst above described.

.drical' pellets in a standard type pelleting ma-f The two catalysts thus asto their activity in hydroiorming a Mid-Continent naphtha having the followlng properties:

Molecular weig 3 182 Bromine numb er.-,. 0.5

In the runs the naphtha was vaporized, mixed with 3.5 mols oi hydrogen f'per 'mol of naphtha and passed .over a-stationary bed of catalyst particles at a temperature 01' 940'1' under a pres- 40 sure or 100' pounds per square inch. The liquid hourly space' 'yelocity based on the naphtha charge referred-to the catalyst space was 1 and theprocessingperiodwasdho produced were tested Catalyst Number Volume per cent liquid. 78. 8 90. 7 Weight per cent liquid recovery-.. 77.35 92.4 Weight r cent carbon 0. 8i 0. 22

umber oi4il F. E. P. Fraction...-- 82.1 66

In the above tabulation column 1 contains the. figures obtained using the catalyst prepared in accordance with the present process, while coltained using the catalyst in the preparation of which the commercial activated alumina was used. The data indicate that the catalyst prepared. in accordance with the present process has considerably higher activity as measured by the higher octane number or the liquid product.

We claimasourinvention:

l. A process for the manufacture of a catalyst comprising alumina and another cataiytically active oxide of a metal, which comprises forming a solution oran' aluminum salt having the .aluml-- num in itscation and a compound oi' said metal containing the metal in the anion and whose I cation-is volatilizable, adding to said solution a 17 1 acid radical of the aluminum salt and said precipitant a salt which is readily volatilizable, subjecting the total reaction mass thus formed to evaporation to reduce the mass to substantial dryness, and heating the residual material sufficient- 1y to convert said metal compound to the oxide.

2. The process as defined in claim 1 further characterized in that said metal is an element in the left-hand column of group VI of the periodic table.

3. The process as defined in claim 1 further characterized in that said metal is an element in the left-hand column of group V of the periodic table.

4. The process as defined in claim 1 further characterized in that said metal in molybdenum.

5. The process as defined in claim 1 further characterized in that said metal is chromium.

6. A process of catalyst manufacture which comprises forming a solution of aluminum chloride and ammonium molybdate, adding to said solution a sufllcient quantity of ammonium hydroxide to obtain a pH value of at least 4, thereby precipitating hydrated alumina, evaporating the resultant total suspension of alumina in amas monium molybdate solution to a substantially solid residue, and heating the residue sufiiciently to decompose the ammonium molybdate to molybdenum oxide.

GLENNM. WEBB. MARVINA. SMITH.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED B'IfATES PATENTS Number Name Date 1,782,857 Miller et al. Nov. 25, 1930 2,184,235 Groll et ai Dec. 19, 1939 2,229,353 Thomas et ai. Jan. 21, 1941 2,249,337 visser et a1. July 15. 1941 2,274,833 Pitzer et ai. Mar. 3, 1942 2,322,863 Marschner et a1. June 29, 1943 2,331,338 Michael et a1. Oct. 12, 1943 2,342,247 Burk Feb. 22, 1944 2,342,248 *Burk Feb. 22, 1944 2,382,394 Bremmer et a1. Aug. 14, 1945 2,395,836 Bates Mar. 5, 1946 FOREIGN PATENTS Number Country Date 504,614 Great Britain Apr. 24, 1939 

